Certain substituted 2,6-diamino-4-methyl-nicotinitriles the corresponding nicotinamides and derivatives thereof

ABSTRACT

2,3,6- AND PREFERABLY ALSO 4-SUBSTITUTED PYRIDINE DERIVATIVES BEARING THE RADICAL OF AMMONIA OR A PRIMARY AMINE IN THE 2- AND 6-POSITIONS. The compounds are eminently suitable as coupling components for the production of azo dyes, the coupling taking place in the 5-position.

.Iadd.

This application is a reissue application of U.S. Pat. No. 3,853,895 issued December 10, 1974, from U.S. Application Ser. No. 328,459, filed January 31, 1973, which in turn is a continuation-in-part of U.S. Application Ser. No. 209,431, filed December 17, 1971 (now abandoned). .Iaddend.

This invention relates to compounds of the formula: ##STR1## where R¹ is hyrogen, alkyl of one to seven carbon atoms or phenyl, the radicals Z independently of one another mean hydrogen or an unsubstituted or substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical and

X is cyano or carbamoyl.

More particularly, the invention relates to compounds of the formula (Ia): ##STR2## IN WHICH R¹ is hydrogen, alkyl of one to seven carbon atoms or phenyl,

X is carbamoyl or cyano and the radicals

R independently of one another are unsubstituted or substituted aliphatic, cycloaliphatic, araliphatic or aromatic radicals and one of the radicals R may be hydrogen and at least one of the radicals R contains an oxygen atom.

Examples of alkyl radicals R¹ are ethyl, n-propyl, isopropyl, butyl, pentyl, α-ethylpentyl and preferably methyl.

Examples of radicals Z or R are alkyl of one to eight carbon atoms which may be interrupted by oxyten atoms and which may bear hydroxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy as substituents, cycloalkyl and polycycloalkyl which may bear hydroxy, chloro, hydroxyalkyl, chloroalkyl or alkyl as substituents, aralkyl of seven to fifteen carbon atoms, phenyl which may bear chloro, hydroxy, alkoxy, alkyl, hydroxyalkoxy or hyroxyalkyl as substituents, or alkenyl, pyrrolidonylalkyl or carboxyalkyl.

Examples of individual radicals Z or R are:

1. UNSUBSTITUTED OR SUBSTITUTED ALKYL:

Ch₃, c₂ h₅, n-C₃ H₇, i-C₃ H₇, n-C₄ H₉, i-C₄ H₉, C₆ H₁₃, ##STR3## CH₂ CH₂ OH, (CH₂)₃ OH, ##STR4## (CH₂)₄ OH, (CH₂)₆ OH, ##STR5## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ OC₂ H₄ OH, (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅, (CH₂)₃ OC₂ H₄ OCH(CH₃)₂, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₂ H₄ C₆ H₅, ##STR6## (CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR7## corresponding radicals in which the groupings ##STR8## are present twice, three times or four times, CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ C₂ OC₃ H₇, CH₂ CH₂ OC₄ H₉, CH₂ CH₂ OC₆ H₅, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR9## (CH₂)₃ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ C₆ H₅, (CH₂)₃ OC₆ H₅, ##STR10## (CH₂)₂ CN, (CH₂)₅ CN, (CH₂)₆ CN, (CH₂)₇ ON or (CH₂)₃ OC₈ H₁₇ and C₆ H₄ CH₃ instead of C₆ H₅

2. unsubstituted or substituted cycloalkyl or polycycloalkyl: ##STR11##

3. aralkyl: ##STR12## and C₆ H₄ CH₃ instead of C₆ H₅.

4. unsubstituted or substituted phenyl:

C₆ h₅, c₆ h₄ ch₃, c₆ h₃ (ch₃)₂, c₆ h₄ och₃, c₆ h₄ oc₂ h₅, c₆ h₄ oh, c₆ h₄ och₂ ch₂ oh or C₆ H₄ Cl,

5. CH₂ CH=CH₂, (CH₂)₂ COOH, (CH₂)₅ COOH and ##STR13## in which n is 2, 3, 4, or 6.

For the production of compounds of formula (I), compounds of formula (II): ##STR14## in which Y is chloro or a radical of the formula NHR, and

X, r and R¹ have the meanings given above may be reacted with an amine of the formula:

R--NH₂.

reaction conditions which affect the exchange of the chlorine atom(s) include the temperature, the amine component, the molar ratio of the reactants and any diluent or solvent or acid-binding agent used. Amines of low boiling point may of course be reacted under superatmospheric pressure. The reaction with the amine is conveniently carried out at elevated temperature, a temperature of from about 0° to 110° C being adequate for the exchange of the first chlorine atom depending on the basicity of the amine, while temperatures in the range from about 60° to 180° C being advantageous for exchange of the second chlorine atom.

Amines of high basicity react more rapidly than those of low basicity; when exchanging the second chlorine atom it is advantageous to use an excess of amine (more than 10 percent), whereas the first chlorine atom reacts immediately with a molar amount of amine. Examples of suitable diluents or solvents which may be added are alcohols such as methanol, ethanol or isopropanol, glycols and glycol ethers such as methyl glycol, ethyl glycol or butyl glycol, hydrocarbons and halohydrocarbons such as benzene, toluene, ethylene chloride, chloroform, trichloroethylene or chlorobenzene, and also acetone, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone or dimethylsulphoxide. The presence of water does not cause any disturbance.

The addition of acid-binding agents is advantageous because then the total amount of amine to be reacted is available for the exchange. Substances which do not themselves react with the chloropyridine derivatives are suitable as acid-binding agents; for example tertiary amines such as triethylamine, tributylamine, triethanolamine, ethyldiisopropylamine, caustic soda solution, sodium carbonate, magnesium oxide or calcium carbonate are suitable. In the case of inexpensive amines, an excess of the amine to be reacted may also serve as acid-binding agent.

Compounds of the formula (Ib); ##STR15## in which R has the meanings given above are of particular industrial significance.

Examples of preferred radicals R containing oxygen are:

Ch₂ ch₂ oh, ch₂ ch₂ ch₂ oh, ##STR16## (ch₂)₃ o(ch₂)₂ oh, (ch₂)₃ o(ch₂)₄ oh, (ch₂)₃ o(ch₂)₆ oh, (ch₂)₄ oh, (ch₂)₆ oh, (ch₂)₂ o(ch₂)₂ oh, ##STR17## ch₂ ch₂ och₃, ch₂ ch₂ oc₂ h₅, ch₂ ch₂ oc₄ h₉, (ch₂)₃ och₃, (ch₂)₃ oc₂ h₅, (ch₂)₃ oc₃ h₇, (ch₂)₃ oc₄ h₉, (ch₂)₃ oc₆ h₁₃, (ch₂)₃ oc₈ h₁₇, ##STR18## (ch₂)₃ oc₂ h₄ och₃, (ch₂)₃ oc₂ h₄ oc₄ h₉, ##STR19## and (CH₂)₃ OC₂ H₄ OC₆ H₅.

Examples of preferred oxygen-free radicals which are preferably used in combination with an oxygen-containing radical R are besides H:

C₂ h₅, c₃ h₇, c₄ h₉, ##STR20## ch₂ c₆ h₅, c₂ h₄ c₆ h₅, c₃ h₇ c₆ h₅, ##STR21## c₆ h₅, c₆ h₄ ch₃, c₆ h₄ och₃.

the new coupling components are outstandingly suitable for the production of azo dyes by reaction with diazotized amines. The dyes which can be obtained in this way are distinguished by excellent fastness properties and by unusual brightness for azo dyes.

The following Examples illustrate the invention. Parts and percentages referred to are by weight unless otherwise stated.

EXAMPLE 1

187 parts of 2,6-dichloro-3-cyano-4-methylpyridine is suspended in 500 parts by volume of methanol. 80 parts of 2-hydroxyethylamine is then added at 40° to 45° C followed by 100 parts of triethylamine. The mixture is stirred for five to six hours at 45° to 50° C, about 250 parts by volume of methanol is distilled off and the residue is diluted with 1000 parts by volume of water. After acidification with 50 parts of concentrated hydrochloric acid, the whole is stirred for 1 hour, the deposited precipitate is filtered off, washed with water until neutral and dried. About 210 parts of a colorless powder of the formula: ##STR22## is obtained. The powder contains a minor amount of a product of the formula: ##STR23## The mixture melts at 115° to 120° C.

125 parts of this powder is stirred with 300 parts by volume of methoxyethylamine for six hours under reflux.

Excess methoxyethylamine is then extensively distilled off so that the temperature may rise to 130° C and the whole is then diluted with 500 parts of water. The mixture is stirred for one hour at 0° to 10° C and the deposited precipitate is filtered off, washed with water and dried. The main product has the formula: ##STR24## and there is a minor amount of a product having the formula: ##STR25## The product is colorless and melts at 75° to 78° C.

EXAMPLE 2

A suspension of 50 parts by volume of methanol, 22 parts of norbornylamine, 37 parts of 2,6-dichloro-3-cyano-4-methylpyridine and 25 parts of triethylamine is stirred for six hours at 40° to 50° C. Then about 200 parts by volume of ice-water is added, the whole acidified to pH 1, and the precipitated product of the formula ##STR26## (which still contains a small proportion of 2-chloro-3-cyano-4-methyl-6-norbornylaminopyridine isomers) is filtered off, washed with water and dried. About 45 parts of a colorless powder is obtained which melts at 110° to 112° C.

45 parts of the moist powder is heated at 130° C to 140° C with 50 parts of the amine of the formula:

H₂ N--CH₂ --CH₂ --O--CH₂ --CH₂ --OH

the water being allowed to evaporate. After stirring for 5 hours at 130° to 140° C the reaction is completed. The whole is allowed to cool and is acidified with 130 parts by volume of acetic acid. A solution of the coupling component mixture of the formulae: ##STR27## and ##STR28## is obtained, the amount of the product of formula (II) being small.

When the mixture thus obtained is coupled with p-nitroaniline a dye is obtained which dissolves in dimethylformamide to give an orange solution.

EXAMPLE 3

A mixture of 300 parts by volume of N-methylpyrrolidone, 150 parts of 2,6-dichloro-3-cyano-4-methylpyridine, 115 parts of p-anisidine and 90 parts of triethylamine is stirred for from six to 7 hours at 70° C. It is then poured while stirring onto 1500 parts of ice-water and acidified with hydrochloric acid to pH 1. About 220 parts of a colorless product of the formula: ##STR29## is obtained which is isolated by filtration, washing with water and drying. The powder contains a minor amount of a product of the formula: ##STR30## The mixture melts at 147° to 150° C.

EXAMPLE 4

50 parts of 2,6-dichloro-3-carbamoyl-4-methylpyridine is stirred with 75 parts of propanolamine-1,3 for 10 hours at 90° C. The mixture is precipitated with water and acidified to pH <O. The insoluble residue is filtered off, washed with water and dried. The colourless powder melts at 210° C and probably has the formula (I): ##STR31## The filtrate has caustic soda solution added to it until the pH is from 5 to 6. A crystalline precipitate is thrown down which probably has the formula (II) ##STR32## This is filtered off, washed with water and dried. The product (II) thus obtained also contains traces of the product of the formula (I) and melts at 150° to 160° C.

If the reaction mixture is precipitated at pH from 6 to 7, a mixture of the two isomers is obtained which has a melting point of about 143° C.

When 2,6-dichloro-3-carbamoyl-4-methylpyridine is treated analogously to the method described in Example 4, mixtures of substituted 2-aminopyridines and 6-aminopyridines are obtained, the amount of 2-amino-3-carbamoyl-4-methyl-6-chloropyridine derivatives being only slightly greater than that of the 6-aminopyridine isomers in question.

The physical properties given in Table 1 relate to mixtures.

                  TABLE 1                                                          ______________________________________                                          ##STR33##                                                                                                  Melting                                                                        point,                                            Number     R.sup.1           ° C.                                       ______________________________________                                                     ##STR34##        115-199                                           6          (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                                120                                               7          C.sub.4 H.sub.9 (n)                                                                              121-122                                           8          C.sub.6 H.sub.13 (n)                                                                             89-90                                             9                                                                                          ##STR35##        140-145                                           10                                                                                         ##STR36##        180-190                                           11         (CH.sub.2).sub.3 OCH.sub.3                                                                       105                                               12         C.sub.3 H.sub.7 (n)                                                                              124                                               13         CH.sub.2 CH.sub.2 OH                                                                             130                                               14         (CH.sub.2 CH.sub.2 O).sub.2 H                                                                    110                                               15         CH.sub.3          >150                                              16         C.sub.2 H.sub.5   143                                               17                                                                                         ##STR37##        190                                               ______________________________________                                    

When 2,6-dichloro-3-cyano-4-methylpyridine is treated by a method analogous to those described in Examples 1 to 3, there are obtained (by exchange of one chlorine atom) mixtures of 2-amino-3-cyano-4-methyl-6-chloropyridine and 2-chloro-3-cyano-4-methyl-6-aminopyridine derivatives, the proportion of the 2-chloro-3-cyano-4-methyl-6-amino isomers being clearly less.

                  TABLE 2                                                          ______________________________________                                          ##STR38##                                                                                                   Melting                                                                        point,                                           Number   R.sup.1              ° C.                                      ______________________________________                                         18       (CH.sub.2).sub.5 COONa                                                                              85 - 91                                          19       (CH.sub.2).sub.5CH.sub.3                                                                            40 - 47                                          20       (CH.sub.2 CH.sub.2 O).sub.2 H                                                                       79 - 83                                          21       (CH.sub.2).sub.2 OCH.sub.3                                                                          90 - 100                                         22       C.sub.4 H.sub.9 (n)  50 - 60                                          23       C.sub.3 H.sub.7 (i)  95 - 105                                         24       (CH.sub.2).sub.3 OCH.sub.3                                                                          75 - 85                                          25                                                                                       ##STR39##           .sup.1                                           26       (CH.sub.2).sub.3 OH  110 - 114                                        27       (CH.sub.2).sub.2 OH  125                                              28                                                                                       ##STR40##           145 - 154                                        29                                                                                       ##STR41##           147 - 149                                        30       H                    225 - 230                                        31                                                                                       ##STR42##           165 - 175                                        32                                                                                       ##STR43##           103 - 105                                        33                                                                                       ##STR44##           Tar                                              34                                                                                       ##STR45##           103                                              35                                                                                       ##STR46##           90 - 92                                          36       (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5                                                          .sup.2                                           37                                                                                       ##STR47##           105 - 110                                        38                                                                                       ##STR48##           170 - 185                                        39                                                                                       ##STR49##           147                                              40                                                                                       ##STR50##           120 - 128                                        41                                                                                       ##STR51##           170                                              42                                                                                       ##STR52##           107 - 110                                        43                                                                                       ##STR53##           .sup.3                                           44                                                                                       ##STR54##           185                                              45       CH.sub.2 CH.sub.2 COOH                                                                              170                                              46       C.sub.14 H.sub.29    62                                               47                                                                                       ##STR55##           130 - 140                                        48                                                                                       ##STR56##           160                                              49       CH.sub.3             140                                              50                                                                                       ##STR57##           80                                               51       (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                               75 - 80                                          52       (CH.sub.2).sub.3 OC.sub.3 H.sub.7 (i)                                                               Oil                                              53       CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                                    118 - 123                                        54       (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                                  Oil                                              55                                                                                       ##STR58##           172                                              56                                                                                       ##STR59##           Oil                                              57                                                                                       ##STR60##           115                                              ______________________________________                                          .sup.1 Greasy product.                                                         .sup.2 Tar becoming solid on prolonged standing.                               .sup.3 Viscous oil.                                                      

When the products set out in Tables 1 and 2 are treated with aliphatic or aromatic amines at temperatures above 100° or 80° C respectively, the corresponding coupling products are obtained.

In the case of pyridine derivatives which contain a carbamoyl group the reaction has to be carried out however at the lowest possible temperature because otherwise hyrolysis and/or decarboxylation of the --CONH₂ group may take place.

                                      TABLE 3                                      __________________________________________________________________________      ##STR61##                                                                     Number                                                                              R.sup.1           R.sup.2               Melting point, °           __________________________________________________________________________                                                  C.                                58   CH.sub.2 CH.sub.2 OH                                                                             CH.sub.3              125 - 130.                        59   CH.sub.2 CH.sub.2 OH                                                                             (CH.sub.2).sub.3 OH   47 - 50.                          60   CH.sub.2 CH.sub.2 OH                                                                             (CH.sub.2).sub.3 OCH.sub.3                                                                           104 - 105.                        61   CH.sub.2 CH.sub.2 OH                                                                             CH.sub.2 CH.sub.2 OH  156.                              62   (CH.sub.2).sub.3 OH                                                                              CH.sub.3              215 (hydrochloride).              63                                                                                   ##STR62##        (CH.sub.2).sub.3 OH   220 - 223.                        64   (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                            H                     Viscous oil.                      65   (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                            (CH.sub.2).sub.3 OH   "                                 66   (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                            (CH.sub.2).sub.3 OCH.sub.3                                                                           "                                 67   (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                            (CH.sub.2).sub.2 OCH.sub.3                                                                           "                                 68   (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                            (CH.sub.2).sub.2 OCH.sub.3                                                                           "                                 69   (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                            (CH.sub.2).sub.3 OH   "                                 70   (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                            (CH.sub.2).sub.2 OH   "                                 71   (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                            (CH.sub.2).sub.3 OH   "                                 72   CH.sub.2 CH.sub.2 OCH.sub.3                                                                      CH.sub.2 CH.sub.2 OCH.sub.3                                                                          75 - 76.                          73   CH.sub.2 CH.sub.2 OCH.sub.3                                                                      CH.sub.2 CH.sub.2 OH  108 - 111.                        74   CH.sub.2 CH.sub.2 OCH.sub.3                                                                      C.sub.6 H.sub.13 (n)  Oil which has green                                                            fluorescence.                     75   CH.sub.2 CH.sub.2 OCH.sub.3                                                                      H                     108.                              76   (CH.sub.2).sub.3OCH.sub.3                                                                        H                     95 - 98.                          77   (CH.sub.2).sub.3 OH                                                                              (CH.sub.2).sub.3 OH   84 - 87.                          78                                                                                   ##STR63##        H                     215 - 220.                        79   "                 CH.sub.2 CH.sub.2 OH  137.                              80   "                 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                              125 - 130.                        81                                                                                   ##STR64##        (CH.sub.2).sub.3 OH   170.                              82   "                 (CH.sub.2 CH.sub.2 O).sub.2 H                                                                        175 - 180.                        83                                                                                   ##STR65##        (CH.sub.2).sub.3 OH   169 - 170.                        84                                                                                   ##STR66##        CH.sub.2 CH.sub.2 OH  155 - 158.                        85   C.sub.6 H.sub.5   CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                        150 (hydrochloride).              86                                                                                   ##STR67##        CH.sub.2 CH.sub.2 OH  173.                              87                                                                                   ##STR68##        CH.sub.2 CH.sub.2 OH  136 - 140.                        88   "                 CH.sub.2 CH.sub.2 OCH.sub.3                                                                          134 - 138.                        89                                                                                   ##STR69##        CH.sub.2 CH.sub.2 OH  90 - 95 esterified with                                                        acetic acid.                      90   "                 CH.sub.2 CH.sub.2 OCH.sub.3                                                                          105.                              91   CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                                 CH.sub.2 CH.sub.2 OCH.sub.3                                                                          60.                               92   CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                                 CH.sub.2 CH.sub.2 OH  167 - 170.                        93   C.sub.4 H.sub.9 (n)                                                                              CH.sub.2 CH.sub.2 OH  Oil having green                                                               fluorescence.                     94   C.sub.4 H.sub.9 (n)                                                                              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                              "                                 95   C.sub.2 H.sub.5   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                              "                                 96   CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                               CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                              "                                 97   (CH.sub.2).sub.5 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                              "                                 98   (CH.sub.2).sub.3OCH.sub.2 CH(CH.sub.3).sub.2                                                     CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                              "                                 99   H                 (CH.sub.2).sub.3O(CH.sub.2).sub.4 OH                                                                 Viscous oil                       100  H                 (CH.sub.2).sub.3O(CH.sub.2).sub.6 OH                                                                 "                                 101  H                 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                                 "                                 102  H                 (CH.sub.2).sub.3OCH.sub.2C.sub.6 H.sub.5                                                             "                                 103  H                 (CH.sub.2).sub.3OCH.sub.2 CH.sub.2 OC.sub.6                                    H.sub.5               "                                 104  H                 (CH.sub.2).sub.3OCH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                    "                                 105  H                 (CH.sub.2).sub.3O CH.sub.2 CH.sub.2OCH.sub.3                                                         "                                 106  H                                                                                                 ##STR70##            "                                 107  H                 (CH.sub.2).sub.3OCH.sub.2 CH.sub.2 OC.sub.4                                    H.sub.9               "                                 108  H                                                                                                 ##STR71##            "                                 109  H                                                                                                 ##STR72##            "                                 110  H                                                                                                 ##STR73##            "                                 111  H                 (CH.sub.2).sub.3 O(CH.sub.2 CH.sub.2 O).sub.2                                  CH.sub.3              "                                 112  H                                                                                                 ##STR74##            "                                 113                                                                                  ##STR75##        H                     "                                 114  H                 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 115  H                 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 116  H                 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                                "                                 117  H                 (CH.sub.2).sub.6 OH   "                                 118  H                 (CH.sub.2).sub.3OC.sub.2 H.sub.4OC.sub.3 H.sub.7                                                     "                                                                              Shade on coupling with                                                          ##STR76##                        __________________________________________________________________________     119  (CH.sub.2).sub.3 OC.sub.6 H.sub.5                                                                CH.sub.2 CH.sub.2 OH  Orange.                           120  (CH.sub.2).sub.3 OC.sub.6 H.sub.5                                                                CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                        "                                 121  (CH.sub.2).sub.3 OC.sub.6 H.sub.5                                                                CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                              "                                 122  (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5                                                       CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                              "                                 123  (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5                                                       (CH.sub.2).sub.3 OH   "                                 124  (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5                                                       CH.sub.2 CH.sub.2 OH  "                                 125                                                                                  ##STR77##        CH.sub.2 CH.sub.2 OH  "                                 126                                                                                  ##STR78##        (CH.sub.2).sub.3 OH   "                                 127  (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                              CH.sub.2 CH.sub.2 OH  "                                 128  (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                              (CH.sub.2).sub.3 OH   "                                 129  (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                             (CH.sub.2).sub.3 OH   "                                 130  (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                             CH.sub.2 CH.sub.2 OH  "                                 131  (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                             CH.sub.2 CH.sub.2 OCH.sub.3                                                                          "                                 132  (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                             CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                                 "                                 133                                                                                  ##STR79##        CH.sub.2 CH.sub.2 OH  "                                 134  "                 (CH.sub.2).sub.3 OH   "                                 135  "                 (CH.sub.2 CH.sub.2 O).sub.2 H                                                                        "                                 136                                                                                  ##STR80##        CH.sub.2 CH.sub.2 OH  "                                 137                                                                                  ##STR81##        (CH.sub.2).sub.3 OH   "                                 138                                                                                  ##STR82##        CH.sub.2 CH.sub.2 OH  "                                 139  "                 (CH.sub.2).sub.3 OH   "                                 140  "                 (CH.sub.2 CH.sub.2 O).sub.2 H                                                                        "                                                                              Melting point, °           __________________________________________________________________________                                                  C.                                141                                                                                  ##STR83##                                                                                        ##STR84##            Viscous oil.                      142                                                                                  ##STR85##        (CH.sub.2).sub.3 OH   "                                 143                                                                                  ##STR86##        (CH.sub.2 CH.sub.2 O).sub.2 H                                                                        "                                 144                                                                                  ##STR87##        (CH.sub.2).sub.2 OCH.sub.3                                                                           "                                 145                                                                                  ##STR88##        (CH.sub.2).sub.3 OCH.sub.3                                                                           "                                 146                                                                                  ##STR89##                                                                                        ##STR90##            "                                 147  (CH.sub.2).sub.6 OH                                                                               ##STR91##            "                                 148                                                                                  ##STR92##                                                                                        ##STR93##            "                                 149  (CH.sub.2 CH.sub.2 O).sub.2 H                                                                     ##STR94##            "                                 150                                                                                  ##STR95##                                                                                        ##STR96##            "                                 151  (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                            (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 152  (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                            (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 153  (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                            (CH.sub. 2).sub.3 O(CH.sub.2).sub.6 OH                                                               "                                 154                                                                                  ##STR97##        CH.sub.2 CH.sub.2 OH  "                                 155                                                                                  ##STR98##        (CH.sub.2).sub.3 OH   "                                 156                                                                                  ##STR99##                                                                                        ##STR100##           "                                 157                                                                                  ##STR101##       (CH.sub.2 CH.sub.2 O).sub.2 H                                                                        "                                 158                                                                                  ##STR102##       (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 159                                                                                  ##STR103##       (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 160                                                                                  ##STR104##       (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                                "                                 161  (CH.sub.2).sub.3 OH                                                                              (CH.sub.2).sub.3 OH   84° bis 87°                                                      C.                                162  (CH.sub.2 CH.sub.2 O).sub.2 H                                                                    (CH.sub.2 CH.sub.2 O).sub.2 H                                                                        Viscous oil.                      163                                                                                  ##STR105##       (CH.sub.2).sub.2 OCH.sub.3                                                                           "                                 164                                                                                  ##STR106##       (CH.sub.2).sub.3 OCH.sub.3                                                                           "                                 165                                                                                  ##STR107##       (CH.sub.2).sub.3OC.sub.3 H.sub.7                                                                     "                                 166  (CH.sub.2 CH.sub.2 O).sub.2 H                                                                     ##STR108##           "                                 167  (CH.sub.2).sub.2 OH                                                                               ##STR109##           "                                 168  (CH.sub.2).sub.3 OH                                                                               ##STR110##           "                                 169                                                                                  ##STR111##                                                                                       ##STR112##           "                                 170                                                                                  ##STR113##                                                                                       ##STR114##           "                                 171                                                                                  ##STR115##                                                                                       ##STR116##           "                                 172  (CH.sub.2).sub.3 OH                                                                              (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 173  (CH.sub.2).sub.3 OH                                                                              (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 174  (CH.sub.2).sub.3 OH                                                                              (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                                "                                 175  (CH.sub.2 CH.sub.2 OH                                                                            (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH                                                                "                                 176  (CH.sub.2 CH.sub.2 OH                                                                            (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 177  CH.sub.2 CH.sub.2 OH                                                                             (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 178  CH.sub.2 CH.sub.2 OCH.sub.3                                                                      (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 179  CH.sub.2 CH.sub.2 OCH.sub.3                                                                      (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 180  (CH.sub.2).sub.3 OCH.sub.3                                                                       (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 181  (CH.sub.2).sub.3 OC.sub.3 H.sub.7                                                                (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 182  (CH.sub.2).sub.2 OCH.sub.3                                                                       (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 183  (CH.sub.2).sub.3 OCH.sub.3                                                                       (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 184  (CH.sub.2).sub.3 OCH.sub.3                                                                       (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 __________________________________________________________________________                                                  Shade on coupling with                                                          ##STR117##                       __________________________________________________________________________     185  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          CH.sub.3              Orange.                           186  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub. 2 OH                                                         C.sub.2 H.sub.5       "                                 187  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          C.sub.3 H.sub.7       "                                 188  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          C.sub.4 H.sub.9       "                                 189  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          C.sub.5 H.sub.11      "                                 190  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          C.sub.6 H.sub.13      "                                 191  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                           ##STR118##           "                                 192  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          CH.sub.2 CH.sub.2 OH  "                                 193  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          (CH.sub.2).sub.3 OH   "                                 194  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                           ##STR119##           "                                 195  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 196  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                           ##STR120##           "                                 197  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                           ##STR121##           "                                 198  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          (CH.sub.2).sub.2 OCH.sub.3                                                                           "                                 199  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          (CH.sub.2).sub.3 OCH.sub.3                                                                           "                                 200  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                                    "                                 201  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          (CH.sub.2).sub.3 OC.sub.3 H.sub.7 (n)                                                                "                                 202  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          (CH.sub.2).sub.3 OC.sub.3 H.sub.7 (i)                                                                "                                 203  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          (CH.sub.2).sub.3 OCH.sub.2 CH(CH.sub.3).sub.2                                                        "                                 204  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                           ##STR122##           "                                 __________________________________________________________________________                                                  Melting point, °           __________________________________________________________________________                                                  C.                                205  CH.sub.2 CH.sub.2 OCH.sub.3                                                                       ##STR123##           116-117.                          206  CH.sub.2CH.sub.2 OH                                                                               ##STR124##           188-189.                          207  CH.sub.2CH.sub.2 OH                                                                              H                     >150.                             208  (CH.sub.2).sub.3COOH                                                                              ##STR125##           185-188.                          209  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                             C.sub.2 H.sub.5       Viscous oil.                      210  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                             C.sub.3 H.sub.7 (n)   "                                 211  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                             C.sub.4 H.sub.9 (n)   "                                 212  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                             C.sub.5 H.sub.11 (n)  "                                 213  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                             C.sub.6 H.sub.13 (n)  "                                 214  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                              ##STR126##           "                                 215  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                              ##STR127##           "                                 216  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                              ##STR128##           "                                 217  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                              ##STR129##           "                                 218  (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                              ##STR130##           "                                 219                                                                                  ##STR131##       CH.sub.2 CH.sub.2 OH  "                                 220  "                 (CH.sub.2).sub.3 OH   "                                 221  "                 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 222                                                                                  ##STR132##       (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 223  "                 (CH.sub.2 O(CH.sub.2).sub.2 OH                                                                       "                                 224                                                                                  ##STR133##       (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 225  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 226                                                                                  ##STR134##       (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 227  "                 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 228                                                                                  ##STR135##       CH.sub.2 CH.sub.2 OH  "                                 229  "                 (CH.sub.2).sub.2 OH   "                                 230  "                 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 231                                                                                  ##STR136##       (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 232  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 233                                                                                  ##STR137##       (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 234                                                                                  ##STR138##       (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 235  "                 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 236                                                                                  ##STR139##       (CH.sub.2).sub.2 O(CH.sub.2 ).sub.2 OH                                                               "                                 237                                                                                  ##STR140##       CH.sub.2 CH.sub.2 OH  "                                 238  CH.sub.2 CHCH.sub.2                                                                              (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 239  CH.sub.2 CHCH.sub.2                                                                              (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 __________________________________________________________________________                                                  Shade on coupling with                                                          ##STR141##                       __________________________________________________________________________     240                                                                                  ##STR142##       C.sub.2 H.sub.5       Orange.                           241  "                 C.sub.3 H.sub.7 (n)   "                                 242  "                 C.sub.4 H.sub.9 (n)   "                                 243  "                 C.sub.6 H.sub.13 (n)  "                                 244  "                 (CH.sub.2).sub.3 OH   "                                 245  "                 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 246  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 247  "                 (CH.sub.2).sub.3 O(CH.sub. 2).sub.4 OH                                                               "                                 248                                                                                  ##STR143##       C.sub.2 H.sub.5       "                                 249  "                 C.sub.3 H.sub.7 (n)   "                                 250  "                 C.sub.4 H.sub.9 (n)   "                                 251  "                 C.sub.6 H.sub.13 (n)  "                                 252  "                 (CH.sub.2).sub.2 OH   "                                 253  "                 (CH.sub.2).sub.3 OH   "                                 254  "                 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                                "                                 255  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 256  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 257                                                                                  ##STR144##       C.sub.2 H.sub.5       "                                 258  "                 C.sub.3 H.sub.7       "                                 259  "                 C.sub.4 H.sub.9       "                                 260  "                 CH.sub.2 CH.sub.2 OH  "                                 261  "                 (CH.sub.2).sub.3 OH   "                                 262  "                 (CH.sub.2).sub.2 O(CH.sub.2 ).sub.3 OH                                                               "                                 263  "                 (CH.sub.2).sub.2 OCH.sub.3                                                                           "                                 264  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 265  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 266                                                                                  ##STR145##       C.sub.2 H.sub.5       "                                 267  "                 C.sub.3 H.sub.7 (n)   "                                 268  "                 C.sub.4 H.sub.9 (n)   "                                 269  "                 C.sub.6 H.sub.13 (n)  "                                 270  H                                                                                                 ##STR146##           Golden yellow.                    271                                                                                  ##STR147##       CH.sub.2 CH.sub.2 OH  Orange.                           272  "                 (CH.sub.2).sub.3 OH   "                                 273  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 274  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                                "                                 275  "                 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                                "                                 276  "                 (CH.sub.2).sub.2 OCH.sub.4                                                                           "                                 277  "                 (CH.sub.2).sub.3 OCH.sub.3                                                                           "                                 278                                                                                  ##STR148##       (CH.sub.2).sub.3 OCH.sub.3                                                                           Orange.                           279  "                 (CH.sub.2).sub.2 OCH.sub.3                                                                           "                                 280                                                                                  ##STR149##       (CH.sub.2).sub.2 OCH.sub.3                                                                           "                                 281  "                 (CH.sub.2).sub.3 OCH.sub.3                                                                           "                                 __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR150##                                                                                                   Shade coupling with                              Number                                                                              R.sup.1                                                                                R.sup.2   R.sup.3                                                                                ##STR151##                                     __________________________________________________________________________     282  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                      CH.sub.2 CH.sub.2 OH                                                                     H       Orange.                                         283  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                      CH.sub.2 CH.sub.2 OH                                                                     C.sub.2 H.sub.3                                                                        "                                               284  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                      (CH.sub.2).sub.3 OH                                                                      C.sub.2 H.sub.5                                                                        "                                               285  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                      (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                    H       "                                               286  CH.sub.2 CH.sub.2 C.sub.5 H.sub.5                                                      (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                    C.sub.2 H.sub.5                                                                        "                                               287  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                      CH.sub.2 CH.sub.2 OH                                                                     C.sub.3 H.sub.7 (n)                                                                    "                                               288                                                                                  ##STR152##                                                                            CH.sub.2 CH.sub.2 OH                                                                     H       41                                              289                                                                                  ##STR153##                                                                            CH.sub.2 CH.sub.2 OH                                                                     C.sub.3 H.sub.7 (n)                                                                    "                                               290                                                                                  ##STR154##                                                                            (CH.sub.2).sub.3 OH                                                                      C.sub.3 H.sub.7 (n)                                                                    "                                               291                                                                                  ##STR155##                                                                            (CH.sub.2).sub.3 OH                                                                      H       "                                               292                                                                                  ##STR156##                                                                            (CH.sub.2).sub.3 OH                                                                      C.sub.2 H.sub.5                                                                        "                                               293  CH.sub.2 CH.sub.2 OH                                                                   CH.sub.2 CH.sub.2 OH                                                                      ##STR157##                                                                            "                                               294  CH.sub.2 CH.sub.2 OH                                                                   CH.sub.2 CH.sub.2 OH                                                                     C.sub.5 H.sub.11 (n)                                                                   "                                               295  CH.sub.2 CH.sub.2 OCH.sub.3                                                            (CH.sub.2 CH.sub.2 O).sub.2 H                                                            C.sub.6 H.sub.5                                                                        "                                               296  (CH.sub.2).sub.3 OCH.sub.3                                                             (CH.sub.2 CH.sub.2 O).sub.2 H                                                            C.sub.6 H.sub.5                                                                        "                                               297  H                                                                                       ##STR158##                                                                              H       Golden yellow.                                  298  H                                                                                       ##STR159##                                                                              C.sub.3 H.sub.7 (n)                                                                    "                                               299  H       (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                    H       "                                               300  H       (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                    H       "                                               __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________      ##STR160##                                                                                                    Shade after coupling with                       Number                                                                              R.sup.1       R.sup.2                                                                                     ##STR161##                                    __________________________________________________________________________     301  CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                         (CH.sub.2).sub.3 OH                                                                         Red.                                           302  CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                             CH.sub.2 CH.sub.2 OH                                                                        Red.                                           303  CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                             (CH.sub.2).sub.3 OH                                                                         Red.                                           304                                                                                  ##STR162##   (CH.sub.2).sub.3 OH                                                                         Red.                                           305                                                                                  ##STR163##   (CH.sub.2).sub.2 OH                                                                         Red.                                           306  (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5                                                   (CH.sub.2).sub.2 OH                                                                         Red.                                           307  (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5                                                   (CH.sub.2).sub.3 OH                                                                         Red.                                           308  (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                         (CH.sub.2).sub.3 OH                                                                         Red.                                           309  (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                         (CH.sub.2).sub.2 OH                                                                         Red.                                           310  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                        (CH.sub.2).sub.2 OCH.sub.3                                                                  Red.                                           311  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                        (CH.sub.2).sub.3 OCH.sub.3                                                                  Red.                                           312  (CH.sub.2).sub.2 OCH.sub.3                                                                   (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Red.                                           313  (CH.sub.2).sub.3 OCH.sub.3                                                                   (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Red.                                           314  H             (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Yellowish red.                                 315  H             (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                       "                                              316  H             (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                       "                                              317  CH.sub.2CH.sub.2 OH                                                                          CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                            Red.                                           318  (CH.sub.2).sub.3 OH                                                                          CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                            Red.                                           319   (CH.sub.2).sub.3 OCH.sub.3                                                                  CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                            Red.                                           320  CH.sub.2CH.sub.2C.sub.6 H.sub.5                                                              (CH.sub.2).sub.3 OCH.sub.3                                                                  Red.                                           321                                                                                  ##STR164##   CH.sub.2 CH.sub.2 OH                                                                        Red.                                           322                                                                                  ##STR165##   (CH.sub.2).sub.3 OH                                                                         Red.                                           323                                                                                  ##STR166##   (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Red.                                           324                                                                                  ##STR167##   CH.sub.2CH.sub.2 OH                                                                         Red.                                           325  "             (CH.sub.2).sub.3 OH                                                                         Red.                                           326  "             (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Red.                                           327  "             (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                        Red.                                           328  C.sub.4 H.sub.9 (n)                                                                          (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH                                                        Red.                                           329  C.sub.4 H.sub.9 (n)                                                                          (CH.sub.2).sub.2 O(CH.sub.2 ).sub.2 OH                                                      Red.                                           330  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                        C.sub.4 H.sub.9 (n)                                                                         Red.                                           331  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                         ##STR168##  Red.                                           332                                                                                  ##STR169##   (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Red.                                           333                                                                                  ##STR170##   (CH.sub.2).sub.3 OH                                                                         Red.                                           334                                                                                  ##STR171##   (CH.sub.2).sub.3 OH                                                                         Red.                                           335  H             (CH.sub.2).sub.2 OH                                                                         Red.                                           336                                                                                  ##STR172##   (CH.sub.2).sub.2 OH                                                                         Bluish red.                                    337  "             (CH.sub.2).sub.3 OH                                                                         "                                              338  "             (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       "                                              339                                                                                  ##STR173##   (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       "                                              340  (CH.sub.2).sub.2 OH                                                                          (CH.sub.2).sub.2 OH                                                                         Red.                                           341  (CH.sub.2).sub.3 OH                                                                          (CH.sub. 2).sub.3 OH                                                                        Red.                                           342  (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                        (CH.sub.2).sub.3 OH                                                                         Red.                                           343  (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                        (CH.sub.2).sub.2 OCH.sub.3                                                                  Red.                                           344  (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                        (CH.sub.2).sub.3 OCH.sub.3                                                                  Red.                                           345  (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH                                                        (CH.sub.2).sub.3 OCH.sub.3                                                                  Red.                                           346  H             (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Yellowish red.                                 347                                                                                  ##STR174##   CH.sub.2CH.sub.2OH                                                                          Red.                                           348  "             (CH.sub.2).sub.3 OH                                                                         Red.                                           349  "             (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Red.                                           350                                                                                  ##STR175##   (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                       Red.                                           351  "             (CH.sub.2).sub.2 OH                                                                         Red.                                           352  "             (CH.sub.2).sub.3 OH                                                                         Red.                                           353                                                                                  ##STR176##    (CH.sub.2).sub.3 OH                                                                        Red.                                           354                                                                                  ##STR177##   (CH.sub.2).sub.2 OH                                                                         Red.                                           355                                                                                  ##STR178##   (CH.sub.2).sub.2O(CH.sub.2).sub.2 OH                                                        Red.                                           356                                                                                  ##STR179##   CH.sub.2CH.sub.2OH                                                                          Red.                                           __________________________________________________________________________

The Examples described in the above Tables are prepared by always first introducing the radical R¹.

EXAMPLE 357

25 parts of the coupling component of the formula: ##STR180## is stirred with 75 parts of 90 percent sulphuric acid for six to eight hours at 80° to 100° C. The reaction mixture is then precipitated on 500 parts of ice, adjusted to pH 4 to 6 by adding caustic soda solution and extracted with ethyl acetate. After the extractant has been evaporated about 20 parts of the coupling component of the formula: ##STR181## is obtained as a dark oil. A red dye is obtained therefrom after coupling with diazotized p-nitroaniline

EXAMPLE 358

30 parts of 2,6-diamino-3-cyano-4-methylpyridine is stirred with 200 parts by volume of concentrated sulphuric acid for ten hours at 50° C. The whole is then allowed to cool, 250 parts of ice is added and it is left overnight. The deposited precipitate is filtered off and washed witht acetone. After drying, 36 parts of a colourless powder of the formula: ##STR182## is obtained which melts at 250° C with decomposition.

The free base of the formula: ##STR183## is obtained from the salt by a conventional method.

                                      TABLE 6                                      __________________________________________________________________________      ##STR184##                                                                                                   Melting                                         Number                                                                              R.sup.1      R.sup.2      point, ° C.                              __________________________________________________________________________     359  C.sub.6 H.sub.5                                                                             C.sub.6 H.sub.5                                                                             128-130                                         360                                                                                  ##STR185##                                                                                  ##STR186##  178                                             361  CH.sub.3     CH.sub.3     140-150                                         362  CH(CH.sub.2).sub.2                                                                          CH(CH.sub.3).sub.2                                                                          118-120                                         363  C.sub.3 H.sub.7 (n)                                                                         C.sub.3 H.sub.7 (n)                                                                         122-123                                         364  CH.sub.2CHCH.sub.2                                                                          CH.sub.2CHCH.sub.2                                                                          77                                              365  C.sub.4 H.sub.9 (n)                                                                         C.sub.4 H.sub.9 (n)                                                                         97                                              366  C.sub.6 H.sub.13 (n)                                                                        C.sub.6 H.sub.13 (n)                                                                        Oil                                             367                                                                                  ##STR187##                                                                                  ##STR188##  193                                             368  H            H            225                                             369                                                                                  ##STR189##                                                                                  ##STR190##  175                                             370  CH.sub.2 C.sub.6 H.sub.5                                                                    CH.sub.2C.sub.6 H.sub.5                                                                     170                                             371  CH.sub.2CH.sub.2C.sub.6 H.sub.5                                                             CH.sub.2CH.sub.2C.sub.6 H.sub.5                                                             110                                             372  C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             .sup.1 205                                      373  C.sub.6 H.sub.5                                                                             C.sub.4 H.sub.9 (n)                                                                         115                                             374  C.sub.6 H.sub.5                                                                             H            (.sup.2)                                        375  C.sub.4 H.sub.9 (n)                                                                         H            100                                             376  C.sub.2 H.sub.5                                                                             C.sub.6 H.sub.5                                                                             218-220                                         377  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                           H            100                                             378                                                                                  ##STR191##                                                                                  ##STR192##  Ca.60                                           379  H            CH.sub.2CH.sub.2C.sub.6 H.sub.5                                                             Ca.100,.sup.1 188                               380  C.sub.8 H.sub.17 (n)                                                                        H            Oil                                             381  C.sub.14 H.sub.29                                                                           H            Ca.90-105                                       382  H                                                                                            ##STR193##  Tar                                             383                                                                                  ##STR194##  H            Tar                                             384  CH.sub.2CH.sub.2CN                                                                          CH.sub.2CH.sub.2CN                                                                          170-176                                         385  CH.sub.2CH.sub.2CN                                                                          CH.sub.2CH.sub.2C.sub.6 H.sub.5                                                             Ca.120                                          386  H            (CH.sub.2).sub.5 CN                                                                         142                                             __________________________________________________________________________      .sup.1 Hydrochloride.                                                          .sup.2 Tarry: becomes solid after prolonged standing.                    

                  Table 7                                                          ______________________________________                                          ##STR195##                                                                                                     Shade when                                                                     coupled with                                   Ex.  X      R.sup.1  R.sup.2                                                                                    ##STR196##                                   ______________________________________                                         387  CH.sub.3                                                                              H        CH.sub.2 CH.sub.2 OH                                                                       Yellowish red.                                388  CH.sub.3                                                                              H        (CH.sub.2).sub.3 OH                                                                        "                                             389  CH.sub.3                                                                              H                                                                                        ##STR197## "                                             390  CH.sub.3                                                                              H        CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                          "                                             391  C.sub.3 H.sub.7                                                                       C.sub.6 H.sub.5                                                                         CH.sub.2 CH.sub.2 OH                                                                       Bluish red.                                   392  C.sub.3 H.sub.7                                                                       C.sub.6 H.sub.5                                                                         (CH.sub.2).sub.3 OH                                                                        "                                             393  C.sub.3 H.sub.7                                                                       C.sub.6 H.sub.5                                                                         (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                      "                                             394  C.sub.3 H.sub.7                                                                        ##STR198##                                                                             (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                      "                                             395  C.sub.3 H.sub.7                                                                        "       CH.sub.2 CH.sub.2 OH                                                                       "                                             396  C.sub.3 H.sub.7                                                                        "       (CH.sub.2).sub.3 OH                                                                        "                                             397  H      C.sub.6 H.sub.5                                                                         (CH.sub.2).sub.3 OH                                                                        "                                             ______________________________________                                    

EXAMPLE 398

190 parts of 2,6-dichloro-3-cyano-4-methylpyridine, 750 parts of isopropanol and approx. 300 parts of ammonia are stirred in an autoclave for 15 hours at 180° C. The mixture is allowed to cool, excess ammonia is evaporated and 450 parts by volume of isopropanol is distilled off. The residue is mixed with approx. 600 parts of water, the pH is adjusted to approx. 0 with concentrated hyrochloric acid and the solution filtered. Then 50 percent caustic soda solution is added until the pH of the mixture is approx. 9, the mixture allowed to cool to 0°-10° C and then filtered, and the residue is washed with water and dried. 130 to 145 parts of a colorless powder of the formula ##STR199## is obtained which melts at 225° C.

EXAMPLE 399

300 parts of 2,6-dichloro-3-cyano-4-methylpyridine is mixed with about 500 parts by volume of liquid ammonia and treated in an autoclave for 2 hours at approx. 80° C. Excess ammonia is allowed to evaporate, the residue is diluted with approx. 2500 parts by volume of water, and the pH is adjusted to 0 to 1 with hydrochloric acid. The insoluble residue is filtered off, washed with water and dried. Approx. 260 parts of a colorless powder of the formula ##STR200## which contains a minor amount of the isomeric 2-chloro-3-cyano-4-methyl-6-aminopyridine and melts at 210° C is obtained.

168 parts of this powder is mixed with about 170 parts of β-hydroxyethylamine and 170 parts by volume of isopropanol. The mixture is heated for 7 to 10 hours under reflux, the solvent is distilled off, the residue is diluted with about 400 parts of water, and the pH is adjusted to 1 to 2. A deep-colored solution of about 192 parts of the coupling component of the formula ##STR201## is obtained, a minor portion of which consists of 2-amino-4-methyl-5-cyano-6-β-hydroxyethylaminopyridine.

A greenish yellow dye may be obtained by coupling with diazotized 2-aminobenzonitrile.

                                      TABLE 8                                      __________________________________________________________________________      ##STR202##                                                                                                Shade when coupled with                             No.                                                                               R.sup.1   R.sup.2   X                                                                                   ##STR203##                                        __________________________________________________________________________     400                                                                               H         CH.sub.3  CN   Golden yellow.                                     401                                                                               H         C.sub.2 H.sub.5                                                                          CN     "                                                402                                                                               H         C.sub.3 H.sub.7                                                                          CN     "                                                403                                                                               H         C.sub.2 H.sub.4 OCH.sub.3                                                                CN     "                                                404                                                                               H         C.sub.2 H.sub.4 OCH.sub.3                                                                CONH.sub.2                                                                          Yellowish red.                                     405                                                                               H         C.sub.3 H.sub.6 OCH.sub.3                                                                CONH.sub.2                                                                            "                                                406                                                                               H         C.sub.3 H.sub.6 OCH.sub.3                                                                CN   Golden Yellow.                                     407                                                                               H         C.sub.4 H.sub.9 (n)                                                                      CN   Yellow orange.                                     408                                                                               H         C.sub.4 H.sub.9 (n)                                                                      CONH.sub.2                                                                          Yellowish red.                                     409                                                                               H         CH.sub.2 CHCH.sub.2                                                                      CN   Golden yellow.                                     410                                                                               H                                                                                         ##STR204##                                                                              CONH.sub.2                                                                          Yellowish red.                                     411                                                                               H                                                                                         ##STR205##                                                                              CN   Orange.                                            412                                                                               H                                                                                         ##STR206##                                                                              CONH.sub.2                                                                          Red.                                               413                                                                                ##STR207##                                                                              CH.sub.2 CH.sub.2 OH                                                                     CONH.sub.2                                                                          Red.                                               414                                                                                ##STR208##                                                                              (CH.sub.2).sub.3 OH                                                                      CONH.sub.2                                                                          Red.                                               415                                                                               CH.sub.2 CH.sub.2 OH                                                                      ##STR209##                                                                              CONH.sub.2                                                                          Red.                                               416                                                                                ##STR210##                                                                              CH.sub.2 CH.sub.2 OH                                                                     CONH.sub.2                                                                          Red. (M.P. 150-153° C.)                     __________________________________________________________________________ 

We claim:
 1. A compound of the formula ##STR211## in which: R¹ is hydrogen, alkyl of one to seven carbon atoms or phenyl;X is cyano or carbamoyl; and each Z, independently of one another, is hydrogen, alkyl of one to eight carbon atoms, hydroxyalkyl of two to eight carbon atoms, cyanoalkyl of two to seven carbon atoms, alkoxyalkyl of two or three carbon atoms in the alkyl and one to eight carbon atoms in the alkoxy, cyclohexoxypropyl, benzyloxypropyl, β-phenyl-ethoxypropyl, phenoxypropyl, tolyloxypropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, hydroxycyclohexyl, β-hydroxyethoxycyclohexyl, norbornyl, hydroxynorbornyl, hydroxymethylnorbornyl, chloromethylnorbornyl, β-hydroxyethylnorbornyl, bicyclooctyl, phenylalkyl or tolylalkyl of one to four carbon atoms in the alkyl, phenyl, phenyl substituted by methyl, methoxy, ethoxy, hydroxy, chloro or β-hydroxyethoxy, allyl, carboxyethyl, carboxypentyl, ω-pyrrolidonylalkyl of two to six carbon atoms in the alkyl, ##STR212## --(CH₂)₂ O(CH₂)₂ OH, --(CH₂)₃ O(CH₂)₄ OH, --(CH₂)₃ O(CH₂)₆ OH, ##STR213## or --(CH₂)₃ (OC₂ H₄)_(n) OT, n being 1, 2, 3 or 4, and T being hydrogen, alkyl of one to four carbon atoms, benzyl, phenylethyl, cyclohexyl, phenyl or tolyl.
 2. A compound as claimed in claim 1 of the formula ##STR214## in which: Z¹ is an oxygen-containing radical selected from the group consisting of --CH₂ CH₂ OH, --CH₂ CH₂ Ch.sub. 2 OH, ##STR215## --(CH₂)₃ O(CH₂)₂ OH, --(CH₂)₃ O(CH₂)₄ OH, --(CH₂)₃ O(CH₂)₆ OH, --(CH₂)₄ OH, --(CH₂)₆ OH, --(CH₂)₂ O(CH₂)₂ OH, ##STR216## --CH₂ CH₂ OCH₃, --CH₂ CH₂ OC₂ H₅, --CH₂ CH₂ OC₄ H₉, --(CH₂)₃ OCH₃, --(CH₂)₃ OC₂ H₅, --(CH₂)₃ OC₄ H₉, --(CH₂)₃ OC₃ H₇, --(CH₂)₃ OC₆ H₁₃, --(CH₂)₃ OC₈ H₁₇, ##STR217## --(CH₂)₃ OC₂ H₄ OCH₃, --(CH₂)₃ OC₂ H₄ OC₄ H₉, ##STR218## and --(CH₂)₃ OC₂ H₄ OC₆ H₅ ; andZ² is hydrogen, an oxygen-containing radical as defined for Z¹ or an oxygen-free radical selected from the group consisting of --C₂ H₅, --C₃ H₇, --C₄ H₉, ##STR219## --CH₂ C₆ H₅, --C₂ H₄ C₆ H₅, --C₃ H₇ C₆ H₅, ##STR220## --C₆ H₅, --C₆ H₄ CH₃ and --C₆ H₄ OCH₃.
 3. the compound of the formula ##STR221##
 4. The compound of the formula ##STR222##
 5. The compound of the formula ##STR223##
 6. The compound of the formula ##STR224## 